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WO2004108647A2 - Production simplifiee d'alcenones - Google Patents

Production simplifiee d'alcenones Download PDF

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Publication number
WO2004108647A2
WO2004108647A2 PCT/EP2004/005466 EP2004005466W WO2004108647A2 WO 2004108647 A2 WO2004108647 A2 WO 2004108647A2 EP 2004005466 W EP2004005466 W EP 2004005466W WO 2004108647 A2 WO2004108647 A2 WO 2004108647A2
Authority
WO
WIPO (PCT)
Prior art keywords
substituted
propyl
alkyl group
alkenone
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2004/005466
Other languages
German (de)
English (en)
Other versions
WO2004108647A3 (fr
Inventor
Eckhard Hausmann
Olaf BÖSE
Johannes Eicher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Fluor GmbH
Original Assignee
Solvay Fluor GmbH
Solvay Fluor und Derivate GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=33482641&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2004108647(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Solvay Fluor GmbH, Solvay Fluor und Derivate GmbH filed Critical Solvay Fluor GmbH
Priority to AT04739287T priority Critical patent/ATE518821T1/de
Priority to PL04739287T priority patent/PL1644306T3/pl
Priority to JP2006508186A priority patent/JP4921964B2/ja
Priority to EP04739287.3A priority patent/EP1644306B2/fr
Priority to DK04739287.3T priority patent/DK1644306T3/da
Publication of WO2004108647A2 publication Critical patent/WO2004108647A2/fr
Publication of WO2004108647A3 publication Critical patent/WO2004108647A3/fr
Priority to US11/294,371 priority patent/US7405328B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups

Definitions

  • the invention relates to a simplified process for the preparation of halogenated alkenone ethers.
  • Halogenated alkenone ethers for example 4-ethoxy-1,1,1-trifluoro-3-buten-2-one, are building blocks in chemical synthesis, see for example EP-0 744 400. They can be prepared by reacting an acid chloride with a Vinyl ethers in the presence of a base, see European patent application cited above; while the base can also be used in excess as a solvent. It is Z. B. N. D. Field and D. H. Lorenz, High Polymer, 1970, page 394, known that the reaction of phosgene with vinyl ethers in the absence of a base leads to polymerization.
  • the object of the present invention is to provide a simplified process for the production of alkenones. This object is achieved by the method of the present invention.
  • the process according to the invention for the preparation of alkenones envisages reacting vinyl ether and carboxylic acid halide, preferably carboxylic acid chloride, with one another in the absence of an acid scavenger and / or in the presence of a stabilizer for the alkenone.
  • acid scavenger includes in particular bases, especially nitrogen bases such as pyridine or secondary and tertiary amines and onium salts, which are described in the non-prepublished international patent application with the application number PCT / EP 03/00913, with this designation no explanation attempt to be connected should.
  • alkenones Preference is given to a process for the preparation of alkenones with halogen, in particular fluorine and / or chlorine substitution on the carboxylic acid radical. Very particular preference is given to alkenones of the formula (I)
  • R 1 -C (O) -C (H) C (H) -OR 2 (I), wherein R 1 is a C 1 -C 4 -alkyl group or a C 1 -C 4 -alkyl group substituted by at least one halogen atom, or wherein R 1 is CF 3 C (O) CH 2 , and R 2 is aryl, substituted aryl, a C1-C4-alkyl group or a C1-C4-alkyl group which is substituted by at least 1 halogen atom, by reacting an acid halide of the formula (II)
  • R 2 has the abovementioned meaning, in the absence of an acid scavenger and / or in the presence of a stabilizer for the alkenone with each other.
  • R 1 preferably represents methyl, ethyl, n-propyl or i-propyl or methyl, ethyl, n-propyl or i-propyl which is substituted by at least 1 fluorine atom.
  • R 1 particularly preferably represents methyl, ethyl or methyl or ethyl substituted by at least 1 fluorine atom.
  • R 1 is CF 3 , CF 2 H, CF 2 Cl, C 2 F 5 , C 3 F 7 or CF 3 C (O) CH 2 .
  • R 2 may be phenyl substituted for aryl, for example phenyl or C 1 -C 4 -alkyl groups and / or halogen atoms.
  • R 2 is linear or branched
  • R 2 is methyl, ethyl, n-propyl or i-propyl.
  • the acid chloride is preferred. With reference to this preferred embodiment, the invention will be further explained.
  • the molar ratio of acid chloride and vinyl ether is suitably between 0.8: 1 and 1: 0.8, especially between 0.8: 1 to 1: 1.
  • the process according to the invention is expediently carried out in two stages. In the 1st stage, the acid halide is added to the vinyl ether. The reaction may be exothermic, so that the reaction mixture may need to be cooled or the reaction is carried out very slowly. If a low-boiling acid halide is used, it is advantageous to use a cooler attachment which condenses the acid halide and allows a return to the reaction mixture. This step is conveniently carried out at -15 ° C to + 50 ° C, preferably -15 ° C to + 30 ° C.
  • the second stage involves the elimination of hydrogen halide.
  • the process according to the invention for the preparation of alkenones of the formula (I) can be carried out at elevated pressure. Ambient pressure or slight negative pressure (down to 0.5 bar) is advantageous because resulting hydrogen halide can be better removed from the reaction mixture. It can be carried out batchwise or partially continuously. Hydrogen halide formed during or after the reaction z. B. by heating or vacuum or both are removed from the reaction mixture.
  • the inventive method comprises three variants: the reaction in the absence of an acid scavenger (this term also includes onium salts), the reaction in the presence of a stabilizer for the desired product (the alkenone), and finally the reaction with both features, namely in the absence of the acid scavenger and the presence of the stabilizer.
  • stabilizers z. B substituted with several alkyl groups phenols, eg. B. by 2 t-butyl groups and an alkyl group having 1 to 3 carbon atoms substituted phenol, in particular 2,6-di-t-butyl-4-methylphenol suitable.
  • the reaction in the presence of a stabilizer for the alkenone to be prepared can also be carried out in the presence of customary acid scavengers such as amines, onium salts or corresponding solvents such as nitriles, sulfoxides or lactams.
  • customary acid scavengers such as amines, onium salts or corresponding solvents such as nitriles, sulfoxides or lactams.
  • a preferred variant provides for the reaction of the starting compounds generally in the absence of an acid scavenger for the alkenone.
  • acid scavenger is defined above.
  • the other of the two preferred variants envisages reacting the starting compounds in the absence of an acid scavenger but in the presence of a stabilizer for the alkenone to be prepared.
  • stabilizers z. B is the above-mentioned, substituted with several alkyl groups phenols, eg. Example by 2 t-butyl groups and an alkyl group having 1 to 3 carbon atoms substituted phenol, in particular 2,6-di-t-butyl-4-methylphenol.
  • reaction mixtures The work-up of the reaction mixtures is carried out by customary methods. For example, one can distill the desired alkenone of the formula (I) from the mixture.
  • Advantage of the method according to the invention is that the work-up is facilitated in the absence of an acid scavenger.
  • the presence of a stabilizer for the alkenone already in the reaction mixture helps to increase the yield.
  • the absence of an acid scavenger in the co-presence of a stabilizer for the alkenone in the reaction mixture can be very favorable for the yield.
  • ETFBO 4-ethoxy-1,1,1-trifluoro-3-buten-2-one
  • the EVE was charged and the TFAC added at room temperature with dry ice cooling. It was then thermolyzed at 80 ° C. The thermolyzed mixture was then distilled at 7 mbar.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Il est possible de produire des éthers d'halogénoalcénones par addition d'halogénures d'acide carboxylique à un éther vinylique et séparation de l'halogénure d'hydrogène. L'amélioration apportée par la présente invention réside dans le fait que cette réaction est conduite en l'absence d'une base et/ou en présence d'un agent stabilisateur pour l'alcénone. Le produit de la réaction se forme avec un rendement élevé.
PCT/EP2004/005466 2003-06-06 2004-05-21 Production simplifiee d'alcenones Ceased WO2004108647A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AT04739287T ATE518821T1 (de) 2003-06-06 2004-05-21 Verfahren zur herstellung von alkenonethern
PL04739287T PL1644306T3 (pl) 2003-06-06 2004-05-21 Sposób produkcji alkenonoeterów
JP2006508186A JP4921964B2 (ja) 2003-06-06 2004-05-21 アルケノンの簡略化した製法
EP04739287.3A EP1644306B2 (fr) 2003-06-06 2004-05-21 Production simplifiee d'alcenones
DK04739287.3T DK1644306T3 (da) 2003-06-06 2004-05-21 Fremgangsmåde til fremstilling af alkenonethere
US11/294,371 US7405328B2 (en) 2003-06-06 2005-12-06 Method for producing alkenone ethers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10325715.2 2003-06-06
DE10325715A DE10325715A1 (de) 2003-06-06 2003-06-06 Vereinfachte Herstellung von Alkenonen

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/294,371 Continuation US7405328B2 (en) 2003-06-06 2005-12-06 Method for producing alkenone ethers

Publications (2)

Publication Number Publication Date
WO2004108647A2 true WO2004108647A2 (fr) 2004-12-16
WO2004108647A3 WO2004108647A3 (fr) 2005-02-24

Family

ID=33482641

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2004/005466 Ceased WO2004108647A2 (fr) 2003-06-06 2004-05-21 Production simplifiee d'alcenones

Country Status (11)

Country Link
US (1) US7405328B2 (fr)
EP (1) EP1644306B2 (fr)
JP (1) JP4921964B2 (fr)
CN (1) CN100471830C (fr)
AT (1) ATE518821T1 (fr)
DE (1) DE10325715A1 (fr)
DK (1) DK1644306T3 (fr)
ES (1) ES2370173T3 (fr)
PL (1) PL1644306T3 (fr)
PT (1) PT1644306E (fr)
WO (1) WO2004108647A2 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7528286B2 (en) 2007-06-29 2009-05-05 Dow Agrosciences Llc 4-Chloro-4-alkoxy-1,1,1-trifluoro-2-butanones, their preparation and their use in preparing 4-alkoxy-1,1,1-trifluoro-3-buten-2-ones
WO2010000871A3 (fr) * 2008-07-04 2010-03-04 Solvay Sa Procédé de préparation d’alcénones
WO2010099922A1 (fr) 2009-03-04 2010-09-10 Syngenta Participations Ag Procédé chimique pour la production d'éthers d'haloalcénones
WO2011003856A1 (fr) 2009-07-06 2011-01-13 Solvay Sa Procédé pour la fabrication de précurseurs halogénés d'alcénones sous des conditions spécifiques
WO2011003860A1 (fr) * 2009-07-06 2011-01-13 Solvay Sa Procédé de fabrication d'alcénones
WO2011003854A1 (fr) 2009-07-06 2011-01-13 Solvay Sa Procédé de fabrication de précurseurs halogénés d'alcénones en présence d'un solvant
WO2012025548A1 (fr) 2010-08-27 2012-03-01 Solvay Sa Procédé pour la préparation d'alcénones
WO2014029786A1 (fr) 2012-08-22 2014-02-27 Solvay Sa Procédé de fabrication d'alcénones
US8957254B2 (en) 2009-07-06 2015-02-17 Solvay Sa Process for chemical synthesis from an alkenone made from a halogenated precursor
WO2017198812A2 (fr) 2016-05-19 2017-11-23 Solvay Sa Procédé de préparation de 5-(1-méthylthio)alkylpyridines substituées en position 2
WO2019043238A1 (fr) 2017-09-04 2019-03-07 Solvay Sa Procédé et intermédiaire de fabrication de chlorure de difluoroacétyle

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2181087B1 (fr) 2007-08-16 2015-10-14 Solvay Sa Procédé de préparation d'esters d'acides 3-oxo-alcanoïques substitués par fluoro en position 4
AU2009265035B2 (en) * 2008-07-01 2011-12-22 Corteva Agriscience Llc Improved process for the preparation of 2-Trifluoromethyl-5-(1-substituted)alkylpyridines
KR20160131129A (ko) 2008-09-30 2016-11-15 솔베이(소시에떼아노님) 할로겐화 환형 화합물의 합성 방법
EP2607343A1 (fr) * 2011-12-22 2013-06-26 Solvay Sa Procédé pour la fabrication de précurseurs halogénés d'alcénones et d'alcénones
WO2015011728A1 (fr) 2013-07-26 2015-01-29 Srf Limited Procédé de production d'éthers d'alcénone
WO2016079122A1 (fr) 2014-11-17 2016-05-26 Solvay Sa Procédé de production d'un composé chimique et appareil associé
CN108884051A (zh) 2016-01-28 2018-11-23 索尔维公司 卤素取代的二酮化合物、吡唑化合物及用于制造吡唑化合物的方法
EP3199522A1 (fr) 2016-02-01 2017-08-02 Solvay SA Dérivés d'aminothioate, leur production et leur utilisation
EP3605700A1 (fr) 2018-07-31 2020-02-05 Solvay Sa Nouveaux composants pour compositions d'électrolyte
EP3605699A1 (fr) 2018-07-31 2020-02-05 Solvay Sa Nouveaux composants pour des compositions d'électrolyte
WO2020025499A1 (fr) 2018-07-31 2020-02-06 Solvay Sa Nouveaux composants pour compositions électrolytiques
EP3605698A1 (fr) 2018-07-31 2020-02-05 Solvay Sa Nouveaux composants pour compositions d'électrolyte
EP3632855A1 (fr) 2018-10-02 2020-04-08 Solvay Sa Procédé permettant de fournir des compositions aqueuses ayant une teneur réduite en composés fluorés organiques
CN112979443A (zh) * 2019-12-13 2021-06-18 浙江蓝天环保高科技股份有限公司 一种三氟甲基丁烯酮类衍生物的连续制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0744400A2 (fr) 1995-05-26 1996-11-27 Ishihara Sangyo Kaisha, Ltd. Procédé pour la préparation de l'acide 4-trifluorométhylnicotinique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3843152B2 (ja) * 1995-08-08 2006-11-08 石原産業株式会社 ４−アルコキシ−１，１，１−トリフルオロ−３−ブテン−２−オンの製造方法
JP3463876B2 (ja) * 2000-10-23 2003-11-05 株式会社日本触媒 ビニルエーテル基含有（メタ）アクリル酸エステル組成物及びその製造方法
WO2003006407A1 (fr) * 2001-07-13 2003-01-23 Kyowa Yuka Co., Ltd. Procédé de production de composé d'éther

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0744400A2 (fr) 1995-05-26 1996-11-27 Ishihara Sangyo Kaisha, Ltd. Procédé pour la préparation de l'acide 4-trifluorométhylnicotinique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
COLLA ET AL., SYNTHESIS, 1991, pages 483 - 486

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7528286B2 (en) 2007-06-29 2009-05-05 Dow Agrosciences Llc 4-Chloro-4-alkoxy-1,1,1-trifluoro-2-butanones, their preparation and their use in preparing 4-alkoxy-1,1,1-trifluoro-3-buten-2-ones
WO2010000871A3 (fr) * 2008-07-04 2010-03-04 Solvay Sa Procédé de préparation d’alcénones
US8519195B2 (en) 2008-07-04 2013-08-27 Solvay Sa Process for the manufacture of alkenones
WO2010099922A1 (fr) 2009-03-04 2010-09-10 Syngenta Participations Ag Procédé chimique pour la production d'éthers d'haloalcénones
US8426650B2 (en) 2009-07-06 2013-04-23 Solvay Sa Process for the manufacture of halogenated precursors of alkenones in the presence of a solvent
WO2011003854A1 (fr) 2009-07-06 2011-01-13 Solvay Sa Procédé de fabrication de précurseurs halogénés d'alcénones en présence d'un solvant
CN102471202A (zh) * 2009-07-06 2012-05-23 索尔维公司 在溶剂存在下制造烯酮的卤化前体的方法
WO2011003860A1 (fr) * 2009-07-06 2011-01-13 Solvay Sa Procédé de fabrication d'alcénones
WO2011003856A1 (fr) 2009-07-06 2011-01-13 Solvay Sa Procédé pour la fabrication de précurseurs halogénés d'alcénones sous des conditions spécifiques
US8957254B2 (en) 2009-07-06 2015-02-17 Solvay Sa Process for chemical synthesis from an alkenone made from a halogenated precursor
CN102471202B (zh) * 2009-07-06 2015-10-07 索尔维公司 在溶剂存在下制造烯酮的卤化前体的方法
WO2012025548A1 (fr) 2010-08-27 2012-03-01 Solvay Sa Procédé pour la préparation d'alcénones
WO2014029786A1 (fr) 2012-08-22 2014-02-27 Solvay Sa Procédé de fabrication d'alcénones
US9365480B2 (en) 2012-08-22 2016-06-14 Solvay Sa Process for the manufacture of alkenones
WO2017198812A2 (fr) 2016-05-19 2017-11-23 Solvay Sa Procédé de préparation de 5-(1-méthylthio)alkylpyridines substituées en position 2
WO2019043238A1 (fr) 2017-09-04 2019-03-07 Solvay Sa Procédé et intermédiaire de fabrication de chlorure de difluoroacétyle

Also Published As

Publication number Publication date
EP1644306B1 (fr) 2011-08-03
DE10325715A1 (de) 2004-12-23
PL1644306T3 (pl) 2011-12-30
WO2004108647A3 (fr) 2005-02-24
ES2370173T3 (es) 2011-12-13
ATE518821T1 (de) 2011-08-15
EP1644306B2 (fr) 2019-12-25
DK1644306T3 (da) 2011-11-21
US20060084813A1 (en) 2006-04-20
US7405328B2 (en) 2008-07-29
CN1832911A (zh) 2006-09-13
CN100471830C (zh) 2009-03-25
JP4921964B2 (ja) 2012-04-25
PT1644306E (pt) 2011-10-19
JP2006527170A (ja) 2006-11-30
EP1644306A2 (fr) 2006-04-12

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